CN111892700A - Saturated polyester type low-shrinkage additive and application thereof - Google Patents
Saturated polyester type low-shrinkage additive and application thereof Download PDFInfo
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- CN111892700A CN111892700A CN202010759489.6A CN202010759489A CN111892700A CN 111892700 A CN111892700 A CN 111892700A CN 202010759489 A CN202010759489 A CN 202010759489A CN 111892700 A CN111892700 A CN 111892700A
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- type low
- saturated polyester
- polyester type
- shrinkage
- low profile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Abstract
The invention discloses a saturated polyester type low-shrinkage additive, which is prepared by the following steps: mixing the polyol with three or more functionality degrees and lactone monomers, and heating to 140-170 ℃ under the protection of nitrogen; then dropwise adding a catalyst, and carrying out reflux reaction for 5-8 hours at the temperature of 150-155 ℃ after dropwise adding; and then cooling to 90-100 ℃, adding a polymerization inhibitor, uniformly stirring, adding an active diluent for dilution after the polymerization inhibitor is completely dissolved, cooling and filtering to obtain the saturated polyester type low-shrinkage additive. The saturated polyester low shrinkage agent has an excellent shrinkage rate control effect, and can enable the colorability of BMC to be better.
Description
Technical Field
The invention belongs to the field of synthesis of high molecular compounds, and particularly relates to a saturated polyester type low-shrinkage additive for a polyester molding compound and application thereof.
Background
Polyester molding compounds (SMC/BMC) are composite materials, typically composed of unsaturated polyester resins, low profile additives, fillers, glass fibers and various adjuvants. Because of its low cost of raw materials, the product has high specific strength, specific modulus, and excellent flame retardance and corrosion resistance, and is widely applied in the fields of automobile traffic, building, electrical and chemical industry, etc. In addition, the SMC/BMC material adopts a compression molding process, can realize automatic production, and has the advantages of safe and environment-friendly production process, high production efficiency and stable product quality. SMC/BMC materials and corresponding compression molding processes have evolved rapidly in recent years.
With the requirement for light weight of automobiles being higher and higher, the requirement of the automobile industry for composite material products is increasing, and higher requirements are put forward on the quality of the glass fiber reinforced plastic composite material products, such as higher requirements on the dimensional stability and the surface smoothness of the products.
Generally, the unsaturated polyester resin can generate 7-10% volume shrinkage during the curing process, so that the product generates large internal stress, and the dimensional stability, the surface smoothness and other properties of the product are negatively influenced. The problem of volume shrinkage during curing of unsaturated polyester resins can be solved by adding low-profile additives. Such as the non-polar low-shrinkage additives such as PE polyethylene powder and PS polystyrene which are developed in the early stage, the low-shrinkage additives have excellent colorability, can be used in molding compound products with various colors, have certain volume shrinkage control capability, usually have the shrinkage rate controlled below 0.2 percent, and can meet the requirements of common molding compound products, but the low-shrinkage additives can not meet the performance requirements of products with particularly high requirements on dimensional precision and surface smoothness, such as automobile exterior trimming parts. The PAVc polyvinyl acetate and PES saturated polyester type low-shrinkage additive can meet the shrinkage control requirement of less than 0.05 percent even zero shrinkage and the surface quality requirement of low waviness on the surface, but the polyvinyl acetate and the saturated polyester type low-shrinkage additive have poor colorability and uneven coloring and cannot be directly used for internally colored products. Therefore, it is required to develop a low shrinkage additive having both an excellent shrinkage control effect and good colorability.
Disclosure of Invention
An object of the present invention is to provide a saturated polyester type low profile additive having an excellent shrinkage control effect and good colorability, in view of the above technical problems to be solved.
It is another object of the present invention to provide a method for preparing the above saturated polyester type low profile additive.
In order to achieve the above object, the present invention provides a saturated polyester type low profile additive, which is prepared by the steps of: mixing the polyol with three or more functionality degrees and lactone monomers, and heating to 140-170 ℃ under the protection of nitrogen; then dropwise adding a catalyst, and carrying out reflux reaction for 5-8 hours at the temperature of 150-155 ℃ after dropwise adding; and then cooling to 90-100 ℃, adding a polymerization inhibitor, uniformly stirring, adding an active diluent for dilution after the polymerization inhibitor is completely dissolved, cooling and filtering to obtain the saturated polyester type low-shrinkage additive.
Preferably, the molar ratio of the polyol to the lactone monomer is 1: 30 to 1: 50.
preferably, the amount of the catalyst added is 0.2 to 0.3 percent of the total weight of the reactants. The total weight of the reactants herein refers to the sum of the weight of the polyol and the lactone monomer.
Preferably, the amount of the reactive diluent added is 50 to 60 percent of the total weight of the polyester. Preferably, the addition amount of the polymerization inhibitor is 0.01-0.02% of the total weight of the polyester. The total weight of the polyester herein refers to the sum of the weights of the polyol, the lactone monomer, and the catalyst.
The invention adopts the polyhydric alcohol with three or more functionality degrees to initiate the ring opening polymerization of lactone to form the branched saturated polyester with relatively regular structure. By controlling the molar ratio of the polyhydric alcohol to the lactone, the saturated polyester type low-shrinkage additive with certain molecular weight and distribution is obtained.
Preferably, the polyhydric alcohol is one or more of glycerol, triethanolamine, trimethylolpropane, ditrimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol. More preferably, the polyol is one or more of ditrimethylolpropane, pentaerythritol, dipentaerythritol.
Preferably, the lactone monomer is one or more of-caprolactone (502-44-3), gamma-caprolactone (695-06-7), -valerolactone (542-28-9), gamma-valerolactone (108-29-2) and lactide. More preferably, the lactone monomer is one or two of-caprolactone and-valerolactone.
Preferably, the catalyst is a titanate-based catalyst or an organotin-based catalyst. More preferably, the catalyst is one or more of tetraisopropyl titanate, tetraisobutyl titanate, tetra-n-butyl titanate, di-n-butyltin dilaurate, stannous octoate, stannous acetate, aluminum triisopropoxide, zinc chloride, zinc lactate, and 4-dimethylaminopyridine.
Preferably, the reactive diluent is one or more of styrene, alpha-methylstyrene, p-methylstyrene, diallyl phthalate, allyl glycidyl ether, allyl glycidyl ester, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, 1, 6-hexanediol diacrylate, and dipropylene glycol diacrylate.
Preferably, the polymerization inhibitor is one or more of methyl hydroquinone, tertiary butyl catechol, tertiary butyl hydroquinone, 2, 5-di-tertiary butyl hydroquinone, 2, 6-di-tertiary butyl-4-cresol and p-benzoquinone.
The invention also provides a method for reducing shrinkage of polyester molding compound products and simultaneously improving coloring performance, which comprises adding the saturated polyester type low-shrinkage additive in the preparation process.
The invention also provides a polyester molding compound product which contains the saturated polyester type low-shrinkage additive.
The invention also provides the application of the saturated polyester type low-shrinkage additive in reducing the shrinkage rate of polyester molding compound products and simultaneously improving the coloring performance.
The saturated polyester type low-shrinkage additive provided by the invention has the advantages of mild synthesis process conditions, stable and controllable reaction process, no three wastes generated in the synthesis process, greenness and environmental protection, and the prepared saturated polyester type low-shrinkage additive has excellent shrinkage control effect and good coloring performance, and can meet the high-quality requirement of high-performance polyester molding plastic products on appearance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the instruments or reagents used in the examples are conventional reagents or instruments in the art, and are conventional products available on the market. Unless otherwise stated, the specific experimental procedures mentioned herein are understood or known by those skilled in the art based on common general knowledge or conventional technical means, and are not described in detail. For the sake of brevity, the parameters of the procedures, steps and equipment used are not described in detail in part of the procedures, it being understood that these are well known to those skilled in the art and are reproducible.
Example 1
25g of pentaerythritol and 620g of caprolactone are sequentially added into a 1L four-neck flask with a thermometer, a stirrer, a nitrogen inlet pipe and a reflux condenser, the temperature is slowly raised to 140 ℃ under the protection of nitrogen, 1.9g of stannous octoate catalyst is dropwise added, and the reflux reaction is carried out for 5 hours at the temperature of 150-155 ℃ after the dropwise addition is finished. Cooling to 90 ℃, adding 0.1g of tert-butyl catechol, stirring uniformly, and adding 326g of styrene for dilution after the polymerization inhibitor is completely dissolved. Cooling and filtering to obtain a nearly water white transparent viscous liquid, namely the saturated polyester type low-shrinkage additive (named as PES-1).
Example 2
33g of ditrimethylolpropane (namely ditrimethylolpropane) and 594g of caprolactone are sequentially added into a 1L four-neck flask with a thermometer, a stirrer, a nitrogen inlet pipe and a reflux condenser, the temperature is slowly raised to 150 ℃ under the protection of nitrogen, then 1.5g of stannous octoate catalyst is dropwise added, and the reflux reaction is carried out for 8 hours within the range of 150-155 ℃ after the dropwise addition is finished. Cooling to 100 deg.C, adding 0.1g tert-butyl catechol, stirring, and diluting with 337g styrene after the polymerization inhibitor is completely dissolved. Cooling and filtering to obtain a nearly water white transparent viscous liquid, namely the saturated polyester type low-shrinkage additive (named as PES-2).
Example 3
28g of dipentaerythritol and 628g of caprolactone are sequentially added into a 1L four-neck flask with a thermometer, a stirrer, a nitrogen inlet pipe and a reflux condenser, the temperature is slowly raised to 170 ℃ under the protection of nitrogen, 2.0g of stannous octoate catalyst is then dropwise added, and after the dropwise addition is finished, the reflux reaction is carried out for 8 hours at the temperature of 150-155 ℃. Cooling to 90 ℃, adding 0.12g of tert-butyl catechol, stirring uniformly, and adding 392g of styrene for dilution after the polymerization inhibitor is completely dissolved. Cooling and filtering to obtain a nearly water white transparent viscous liquid, namely the saturated polyester type low-shrinkage additive (named as PES-3).
Comparative example
LY-S19803 (available from Zhaoqing Futian chemical industries, Ltd.) is a commercially available saturated polyester low shrinkage agent of conventional properties, added here to the comparative example for use as a control.
BMC pellets were prepared in the proportions shown in Table 1.
Table 1: bulk Molding Compound (BMC) bulk material ratio
Note: the commercially available resin with the product model number LY-S28806 is purchased from Zhaoqing Futian chemical industry Co., Ltd and is o-benzene type unsaturated polyester resin.
The prepared BMC agglomerate is pressed into plates under the condition of 150 ℃/3min and processed into various detection samples, the detection method is carried out according to the national standard, and the detection results of various properties are shown in the following table 2.
Table 2: test results of sample Properties
| Inspection item | Example 1 | Example 2 | Example 3 | Comparative example |
| Tensile Strength (MPa) | 40.4 | 33.2 | 37.7 | 33.7 |
| Modulus of elasticity in tension (10)4MPa) | 1.17 | 1.23 | 1.22 | 1.17 |
| Flexural Strength (MPa) | 106.0 | 98.3 | 86.0 | 94.6 |
| Flexural modulus of elasticity (10)4MPa) | 1.34 | 1.24 | 1.20 | 1.22 |
| Impact toughness (kJ/m)2) | 35.1 | 32.8 | 27.4 | 28.6 |
| Shrinkage (%) | 0.0305 | 0.0254 | 0.0292 | 0.0409 |
| 60 degree gloss | 86.7 | 84.4 | 80.1 | 78.5 |
| The color difference is great | 3.3 | 3.1 | 3.7 | 5.8 |
Note: in contrast test, the plate made of the conventional polystyrene low shrinkage agent is used as a standard plate, and the plate made of the low shrinkage agent in examples 1-3 and the comparative example has contrast color difference with the standard plate, wherein the larger the numerical value is, the larger the color difference is;
therefore, the saturated polyester low shrinkage agent disclosed by the invention has an excellent shrinkage control effect and can enable the colorability of BMC to be better.
Claims (10)
1. A saturated polyester type low-shrinkage additive is characterized by being prepared by the following steps: mixing the polyol with three or more functionality degrees and lactone monomers, and heating to 140-170 ℃ under the protection of nitrogen; then dropwise adding a catalyst, and carrying out reflux reaction for 5-8 hours at the temperature of 150-155 ℃ after dropwise adding; and then cooling to 90-100 ℃, adding a polymerization inhibitor, uniformly stirring, adding an active diluent for dilution after the polymerization inhibitor is completely dissolved, cooling and filtering to obtain the saturated polyester type low-shrinkage additive.
2. The saturated polyester type low profile additive according to claim 1, wherein the molar ratio of the polyol to the lactone monomer is 1: 30 to 1: 50.
3. the saturated polyester type low profile additive according to claim 1, wherein the catalyst is added in an amount of 0.2 to 0.3% by weight based on the total weight of the reactants.
4. The saturated polyester type low profile additive according to claim 1, wherein the reactive diluent is added in an amount of 50 to 60% by weight based on the total weight of the polyester.
5. A saturated polyester type low profile additive according to any of claims 1 to 4, wherein the polyol is one or more of glycerol, triethanolamine, trimethylolpropane, ditrimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol.
6. A saturated polyester type low profile additive according to any of claims 1 to 4, wherein the lactone monomer is one or more of-caprolactone, γ -caprolactone, -valerolactone, γ -valerolactone, lactide.
7. The saturated polyester type low profile additive according to any one of claims 1 to 4, wherein the catalyst is a titanate type catalyst or an organotin type catalyst.
8. Use of a saturated polyester type low profile additive according to any of claims 1 to 7 for reducing shrinkage and at the same time improving the colorability of polyester molding compounds articles.
9. A polyester molding compound article comprising the saturated polyester type low profile additive of any one of claims 1 to 7.
10. A method for reducing shrinkage and simultaneously improving colorability of polyester molding compounds articles, characterized by: the saturated polyester type low profile additive of any one of claims 1 to 7 is added during the preparation of the polyester molding compound article.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010759489.6A CN111892700B (en) | 2020-07-31 | 2020-07-31 | Saturated polyester type low-shrinkage additive and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010759489.6A CN111892700B (en) | 2020-07-31 | 2020-07-31 | Saturated polyester type low-shrinkage additive and application thereof |
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| CN111892700B CN111892700B (en) | 2023-08-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61293256A (en) * | 1985-06-20 | 1986-12-24 | Daicel Chem Ind Ltd | Shrinkage controlling agent |
| US4663429A (en) * | 1984-07-31 | 1987-05-05 | Daicel Chemical Industries, Ltd. | Process for producing lactone polymer and an anti-shrinking thermosetting resin composition having formulated therein said lactone polymer as an anti-shrinking agent |
| CN102206311A (en) * | 2011-04-22 | 2011-10-05 | 常州华科树脂有限公司 | Saturated polyester for sheet moulding compound or bulk molding compound (SMC/BMC) low-shrinking agent and preparation method thereof |
-
2020
- 2020-07-31 CN CN202010759489.6A patent/CN111892700B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4663429A (en) * | 1984-07-31 | 1987-05-05 | Daicel Chemical Industries, Ltd. | Process for producing lactone polymer and an anti-shrinking thermosetting resin composition having formulated therein said lactone polymer as an anti-shrinking agent |
| JPS61293256A (en) * | 1985-06-20 | 1986-12-24 | Daicel Chem Ind Ltd | Shrinkage controlling agent |
| CN102206311A (en) * | 2011-04-22 | 2011-10-05 | 常州华科树脂有限公司 | Saturated polyester for sheet moulding compound or bulk molding compound (SMC/BMC) low-shrinking agent and preparation method thereof |
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